Quaternary ammonium derivatives of alcohol amine compounds



Patented Feb. 13, 1940 QUATERNARY AMMONIUM DERIVATIVES F .ALCOHOL AMINE COMPOUNDS Albert K; Epstein and Morris Katzman, Chicago,

Ill., assignors to The Emulsol Corporation, Chicago, Ill.

No Drawing. Application August 3, 1988, Serial No. 222,778

13 Claims. (01. 260-295) This invention relates to new chemical comsulphate, sulphonic, phosphate, carboxyl, nitrile, pounds of the quaternary ammonium type which and the like, as will be pointed out hereinafter, are characterized by possessing interface modifybut it is particularly preferred that it be unsubing properties rendering the same highly useful stituted aliphatic or fatty and contain from eight for the purposes for which such agents are emto eighteen carbon atoms. The radical alk" and ployed in the various arts. residue X may likewise contain substituent At least most of the novel compounds are, in groups such as those mentioned and the sequence general, reaction products preferably of tertiary of carbon atoms therein may be interrupted by v nitrogenous bases with halogeno-carboxylic es- 0, S, C=O, NH, NR where R is alkyl, and the i0 ters of higher molecular weight ethers or esters like. of alcohol amines. Of particular utility are the reaction products Many of the compounds falling within the of tertiary nitrogenous bases, such as pyridine, scope of this invention may be represented by with lower molecular weight h'alogeno-monocarthe general formulae boxylic acid esters of higher molecular weight fatty acid esters of alkylolamines, the higher 0R molecular weight fatty acid radical of which Q contains at least four but particularly from twelve to eighteen carbon atoms.

1 In order that the nature of the invention may become more apparent, there are listed herein- 20 below representative compounds which fall within the scope of the invention:

wherein alk is alkylene or arylene, for example, (1) ethylene or phenylene, R. is an organic radical containing preferably at least six carbon atoms, 7 X is a hydrocarbon or substituted hydrocarbon 0 O1 residue, Q is a quaternary ammonium radical,

A is an anion, and at least one of the three indicated valence bonds attached to nitrogen is satisfied by a radical of the class consisting of (2) H I alkyls, cycloalkyls, allgvlols, aralkyls, aryls, aralcflH4o-C"-CH2 N kylols, and the radical of a heterocyclic ring of 4;

which the nitrogen is a member, and R is a 35 member selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkylol, (alk-OR), G1Hlo-bCuHa and (a) N- :Hs lm O A\ l C2135 where alk, R, X, N and A CHg-CH2CH2CH3O- -G7Hl5 have the foregoing significance, and w is a small (4) 45 whole number, preferably one or two. r rC rCHr-0-G-CH:NC4 i By the term quaternary ammonium radical I we mean one containing a pentavalent nitrogen wherein four valences are satisfied by carbon (5) and the fifth valence by an anion. N-H2C-c-0-0lH4 thHro-c-cuma 59 The radical R in the above formulae may be N-om-om-N of aliphatic, cycloaliphatic, aromatic or aromatic-aliphatic character. and may contain substituent groups such as amino, hydroxy, halogen,

While the above examples represent single substances, it will be understood that, in practice, it is, in general, more advantageous to employ mixtures of any two or more thereof with or without diluents.

The following examples are illustrative of methods which have been found suitable for preparing various of the compounds which are disclosed herein. It will be appreciated that other m'ethods may be utilized, that the proportions of reacting ingredients, times of reaction, order of steps, and temperatures may be varied and that supplementary processes of purification and the like may be resorted to wherever found desirable or convenient. These and other variations and modifications will be evident to those skilled in the art in the light of the guiding principles which are disclosed herein.

Example A The reaction mass had good foaming and frothing characteristics and was useful in ore flotation processes as well as for the general purposes hereinafter set forth.

-If desired, the product may be'purified by extraction of the excess pyridine with petroleum ether followed by drying the residue.

Example B 27.4 grams of the monocaprylic acid ester of triethanolamine, dissolved in 40.0 grams of pyridine, were reacted with 23.4 grams of chloracetyl chloride following thesame procedure described in Example A. The reaction product contained a substantial proportion of a chemical compound corresponding to the formula It possessed properties similar to those of the product of Example A.

Example C 33.2 grams of the monolauric acid ester of triethanolamine, dissolved in 40 grams of pyridine, were reacted with 22.8 grams of chloracetyl chloride following the procedure of Example A. The

grees C., the vacuumbeing maintained.

reaction product contained a substantial proportion of a compound having the formula The properties were similar to those of the previously described products.

Example D (l) 668 grams of coconut oil, 564 grams of commercial triethanolamine, and 0.6 gram of potassium hydroxide were placed in a flask, the flask was evacuated to an absolute pressure of 10 to 40 mm. of mercury, heated to 125 degrees C., and then steam at degrees C. was passed directly into the reaction mixture and heat was applied to maintain the temperature of the reaction mass at about 1'75 degrees C. to 250 de- This temperature was maintained for about 1 hour, steam being continuously passed through the reaction mixture. The reaction mixture was then cooled very quickly by immersion of the flask in an ice bath and the passage of steam was continued until a temperature of about degrees C. was reached. The steam was then shut off but the quick cooling or refrigeration was continued until a temperature of about 60 degrees C. to 70 degrees C. was reached after which the product was allowed to cool in the atmosphere. The final product was a clear, light straw or amber colored liquid essentially free of odor. It consisted essentially of coconut oil mixed fatty acid monoesters of triethanolamine.

(2) 1'70 grams of the product prepared in part (1) hereof were mixed with 95 grams of chloracetic acid and the resulting mixture was heated for two hours at degrees C. to degrees C. It was then cooled to about 40 degrees C. or 50 degrees C.

(3) 50 grams of the product of part (2) hereof, consisting substantially of the monochloracetic acid ester of the coconut oil mixed fatty acid mono-esters of triethanolamine, were mixed with 10 grams of pyridine and the mass was allowed to stand over night. The final product, from which excess pyridine may be removed by extraction with petroleum ether, contained a substantial proportion of compounds having the formula is the acyl radical corresponding to the fatty acids present in the coconut oil mixed fatty acids. The properties of the product were similar to those previously described.

It is, of course, clear that methods other than those described may be employed for producing chloracetic acid,

more, the order of reacting the ingredients may be modified as will be apparent to those skilled in the art. 7

Instead of initially producing, for example, the higher fatty acid ester of triethanolamine and then reacting with chloracetyl chloride or the like in the presence of pyridine or similar tertiary base, the higher fatty acid radical may be introduced subsequently to the introduction of the quaternary ammonium group by reaction with a higher fatty acid halide or the like. Thus, for example, an alcohol amine such as triethanolamine may be reacted with chloracetyl chloride in such proportions as to esterify one or more hydroxy groups, and with pyridine to produce the quaternary ammonium derivative, leaving free at least one triethanolamine hydroxy group. The resulting quaternary ammonium derivative may then be isolated and purified or reacted in the impure state but in dry form with an equivalent amount of a long chain or higher molecular weight acyl halide to esterify the remaining free hydroxy group.

In some cases, hydrogen attached to nitrogen may be connected to. a higher molecular weight organic radical such as represented by R, so as to form amides, as illustrated by formulae (19), (21) (22) and (23) in the list of compounds shown hereinbefore. In at least certain cases, these compounds function similarly to those wherein a higher molecular weight or lipophile radical is attached at an hydroxy group of the alcohol amine to form an ether or ester.

In those cases where a tertiary alcohol amine, such as triethanolamine, tripropanolamine or the like is employed, it is clear, of course, that esters only can be formed by reacting the same with chloracetyl chloride, higher molecular weight fatty acids or their acyl halides or the like. In the case of such reactions wherein primary and secondary alcohol amines, such as monoethanolamine or diethanolamine, are employed, mixtures of amides and esters usually result, in many cases the amides preponderating. To bring about more complete ester formation with the halogeno-carboxylic acids or their halides, should such be desired, the following procedure may be employed: To monoethanolamine, for example, an aldehyde such as formaldehyde, benzaldehyde or the like may be added, this serving to block the amino group. The resulting mixture may then be reacted with chloracetyl chloride or the like whereby the corresponding ester is produced. The resulting reaction product may then be treated with dilute acid solution, for example, weak hydrochloric acid, under mild conditions, to free the amino group, and then the reaction with an acyl halide such as lauroyl chloride and the tertiary base may be carriedout.

The higher molecular weight organic radical represented by R in the general formula set forth hereinabove may be derived from various sources. Such sources include, for example, straight chain and branched chain higher molecular weight carboxylic, aliphatic, and fatty acids, saturated and unsaturated, such as caprylic acid, caproic acid, capric acid, sebacic acid, behenic acid, arachidic acid, cerotic acid, erucic acid, melissic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, lauric acid, myristic acid, palmitic acid, mixtures of any two or more of the above mentioned acids or other acids, mixed higher fatty acids derived from animal or vegetable sources, for example, lard, coconut oil, rapeseed oil, sesame the novel compounds of this invention. Further oil, palm kernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow, soya bean oil, peanut oil, castor oil, seal oil, whale oil, shark oil, partially or completely hydrogenated animal and vegetable oils such as those mentioned; hydroxy and alpha-hydroxy higher aliphatic and fatty acids such as i-hydroxy stearic acid, dihydroxystearic acid, alpha-hydroxy stearic acid, alphahydroxy palmitic acid, alpha-hydroxy lauric acid, alpha-hydroxy coconut oil mixed fatty acids, and

the like; fatty acids derived from various waxes such as beeswax, spermaceti, montan wax, and carnauba wax and carboxylic acids derived, by oxidation and other .methods, from petroleum; cycloaliphatic and hydroaromatic acids such as hexahydrobenzoic acid, resinic acids, naphthenic acid and abietic acid aromatic acids such as phthalic acid, benzoic acid, naphthoic acid, pyridine carboxylic acids; hydroxy aromatic acids such as salicyclic acid, hydroxy benzoic and naphthoic acids, and the like; and substitution and addition derivatives such as amino, halogen, hydroxy, sulphate, sulphonic, phosphate and the like substitution and addition derivatives of the aforementioned carboxylic substances. It will be understood that mixtures of any two or more of saidacids may be employed if desired.

In those cases where higher molecular weight ethers are prepared, the higher molecular weight organic radical may be derived from alcoholates of alcohols corresponding to the higher molecular weight acids referred to hereinabove.

The alcohol amines which provide, in part, the

linkage between the higher molecular weight group represented by R and the quaternary ammonium radical may be selected from a large class and include secondary and tertiary alcohol amines and alkylolamines, symmetrical and unsymmetrical, normal and isoderivatives, such as diethanolamine, triethanolamine and mixtures thereof such as occur in the so-called commercial triethanolamine, monoethyl diethanolamine, tripropanolamine, dipropanolamine, dibutanolamine, tributanolamine, dipentanolamine, trihexanolamine, trilauroylamine, trihexadecylolamine, N-cyclohexyl dibutanolamine, diethanolaniline, monoethyl dipropanolamine, triethanol methyl ammonium hydroxide, diethanolamine cyclohexylamine, monobutyl diethanolamine, di-ethanol methyl amine, secondary and tertiary alkylolamines of other monoor polyvalent alcohols such as glycols, glycerol, sugars and sugar alcohols such as sorbitol, alkylol polyamines such as alkylol derivatives of ethylene diamine, diethylene triamine and tri-ethylene tetra-amine, arylol amines such as N-phenyl diethanolamine and the like.

The halogeno-carboxylic acids and other derivatives thereof such as the halides which are reacted with the tertiary amine and the higher molecular weight fatty acid esters of the alkylolamine or the like, such as the mono lauric acid ester of triethanolamine, are preferably those containing less than eight carbon atoms, and may be selected from a relatively large class including halogeno-, mono-, di-, and poly-carboxylic acids such as chloracetic acid, chloracetyl chloride, bromacetic acid, bromacetyl bromide, iodo acetic acid, alpha-chlor propionic acid, alpha-chlor butyric acid, alpha-bromo capric acid, monochlor succinyl chloride, dichlor succinyl chloride, monochlor succinic acid, dichlor succinic acid, monoand di-brom glutaric acid and the corresponding glutaryl bromides, nitro-chloro-benzoyl chlorides, and the like. Of particular utility are monochloracetyl chloride and mono-bromacetyl bromide.

The anion represented by the letter "A in the .general formulaillustrating the novel reagents organic nitrogenous bases as, for example, alcohol amines and alkylolamines, aralkyloland tertiary amines including triethanolamine and mixtures thereof such as, for example, present in so-called commercial triethanolamine, tripropanolamine, tributanolamine, tripentanolamine,

trihexanolamine, triglycerolamine, dibutyl ethanolamine, diethanol ethyl amine, cyclohexyl diethanolamine, diethanol aniline, alkylol, polyamines such as alkylol derivatives of ethylene diamine, dimethyl monoethanolamine, diethyl monopropanolamine, alkylamines such .as triethyl amine, tripropyl amine, tributyl amine, monohexyl amine, diethylhexylamine, aromatic and heterocyclic bases such as tribenzylamine, di cyclohexyl-aniline, pyridine, alkyl pyridines such as methyl-pyridine, quinoline, quinaldine, nico tine, and homologues and derivatives or substitution products thereof; mixtures of any two or more thereof and the like. It will be understood that these organic bases, as in the case of triethanolamine, for example, may be employed in pure, impure, or commercial form.

It will be understood that by varying the molal ratios of the reacting ingredients, products of variable character may be produced. Thus, for example, the monolauric acid ester of triethanolamine may be reacted with one or more mols of a halogeno-carboxylic acid halide or the like and with one or more mols of pyridine or similar tertiary amines. All of the products, however, have surface modifying characteristics enabling their use for various of the functions hereinafter set forth.

The compounds of this invention have utility in various arts in which interface modifying agents are employed. They are resistant to precipitation by calcium and magnesium salts and are compatible with acid and alkali media. They may be utilized in the textile and related industries wherein they function for softening, wetting, detergent, emulsifying, penetrating, dispersing, frothing and foaming purposes. The

textiles, the treatment of which with the agents of the present invention is rendered effective, comprise natural products such as cotton, wool, linen and the like as well as the artificially produced fibres (and fabrics), such as rayon, cel-.

lulose acetates, cellulose ethers and similar ar tificial products. It will be understood, of course, that the agents may be used in aqueous andother media either alone or in combination with other suitable salts of organic or inorganic character or with other interface modifying agents. In the dyeing of textiles they may be employed as assistants in order to bring about even level shades. They may be used in the leather industry as wetting agents in soaking, dyeing, tan

. ning and the softening and other treating baths for hides and skins. Their utility as emulsifying agents enables them to be employed for the 1 preparation of emulsions which may be used for insecticidal, fungicidal and for similar agriculture purposes. They have utility in the preparation of cosmetic creams ,such ascold creams, vanishing creams, tissue lcreams,shaving creams of the brushless and lathering type and similar cosmetic preparations.. Another useto, which the agents of the'present invention may be placed is for the treatmentbf. paper where they may be employed, for example, as penetrating agents in the cookingpf the paper ;pu lp. or the like. Their capillary or interfacial tension reducing properties enables them to be employed in the fruit and vegetable industry in order to effect the removal from fruits and the like of arsenical and similar sprays. They possess, marked utility in the ore dressing industry wherein they function effectively in froth flotation processes, particularly for the separation of silica from ores containing the same. Their interface modifying properties also permit their use in lubricating oils and the like enabling the production of effective boring oils, cutting oils, drilling oils, wire drawing oils, extreme pressure lubricants and the like. They may also be used with effect in the preparation of -metal and furniture polishes, shoe p01ishes,"in rubber compowhich are encountered in oil-field operations, and for various other purposes which will readily occur to those versed in the art in the light of the disclosure herein.

As detergents, they may be employed for the preparation of shampoos, dentifrices and the like. In general, they may be dissolved in water or aqueous media and utilized in that form or, in the case of solid products, they may be packaged and sold in such form preferably mixed with diluents. They may also be utilized for commercial laundering and washing operations with marked advantage.

The products of the present invention may be employed alone or together with lesser or greater quantities of inorganic or organic compounds. Thus, for example, they may be employed together with salts such as sodium chloride, alkali metal phosphates including pyrophosphates and tetraphosphates, sodium sulphate, alums, perborates such as sodium perborate, and the like. They may be utilized in alkaline or acid media in the presence of sodium carbonate, sodium bicarbonate, dilute acids such as hydrochloric, sulphurous, acetic and similar inorganic and organic acids. They may also be employed in the presence of such diverse substances as hydrophillic gums including pectin, tragacanth, karaya, locust bean, gelatin, arabic and the like, glue, vegetable, animal, fish and mineral oils, solvents such as carbon tetrachloride, monoethyl ether of ethylene glycol, monobutyl ether of ethylene glycol, monoethyl and monobutyl ethers of diaethylene glycol, cyclohexanol, and the like. They phonate; sulpho-carboxylic acid esters of higher molecular weight alcohols such as lauryl sodium sulphoacetate, dioctyl sodium sulpho-succinate, dilauryl potassium sulpho-glutarate, lauryl triethanolamine sulpho-acetate, and the like; sulphuric and sulphonic derivatives of condensation products of alkylolamines and higher fatty acids; phosphoric, pyrophosphoric and tetraphosphoric acid esters of higher molecular weight alcohols; Turkey-red oils; compounds of the type of isopropyl naphthalene sodium sulphonate, and other classes of wetting agents.

It will be understood that the products may be employed in the form of impure reaction mix tures containing substantial proportions of. the effective interface modifying agent or agents or, if desired, for any particular purposes, purification procedures may be employed to produce pure or substantially pure products. Those versed in the art will be familiar .with the types of purification methods which may be employed with advantage herein, particularly in.the light'of the disclosures made hreinabove.

Wherever the term higher, is employed. as referring to higher molecular weight acids or the like, it will be understood to cover compounds or radicals having at least six carbon atoms unless otherwise specifically stated.

What we claim as new and desire to protect by Letters Patent of the United States is:

1. Quaternary ammonium chemical compounds corresponding to the formula wherein alk is alkylene, R is an organic radical containing at least six carbon atoms, X is a hydrocarbon residue, A is an anion, and the three indicated valence bonds attached to nitrogen are satisfied by radicals of the class consisting of alkyls, cycloalkyls, alkylols, aralkyls, aryls, aralkylols, and the radical of a heterocyclic ring of which the nitrogen is a member, and R is a member selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkylol, (alkOR) and where wherein alk is alkylene, R. is an aliphatic acyl radical containing from 6 to 18 carbon atoms, X is a hydrocarbon residue containing less than 6 carbon atoms, A is halogen, and the three indicated valence bonds attached to nitrogen are satisfled by radicals of the class consisting of .allgvls, cycloalkyls, alkylols, aralkyls,- aryls, aralkylols, and the radical of a heterocyclic ring of which the nitrogen is a member, and R is a member selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkylol, (alk--OR) and where and A have the foregoing significance.

3. Quaternary ammonium chemical compounds corresponding to the formula v and 1; have the foregoing significance.

%. Chemical compounds corresponding to the formula I wherein A is halogen.

5. A method of preparing quaternary ammonium compounds which comprises interacting a tertiary nitrogenous base, a member selected from the group consisting of halogeno-carboxylic acids and halides thereof, and a member selected from the group consisting of higher molecular weight ethers andesters of alcohol amines.

6. A method of prepaing quaternary ammonium compounds which comprises interacting a tertiary nitrogenous base, a member selected from the group consisting of aliphatic halogeno-monocarboxylic acids and halides thereof, containing not more than 6 carbon atoms, and a higher molecular weight fatty :acid ester of a tertiary alcohol amine. 1

"l. A method of preparing quaternary ammonium compounds which comprises interacting a tertiary nitrogenous base, a member selected from the group consisting of halogeno-acetic acid and halides thereof, and a member selected from the group consisting of monoand dihigher molecular weight fatty acid esters of triethanolamine.

8. A method of preparing quaternary ammonium compounds which comprises interacting pyridine, chloracetyl chloride, and a member selected from the group consisting of monoand dihigher molecular weight fatty acid esters of triethanolamime, the higher molecular weight wherein alk is a member selected from the group consisting of alkylene and arylene, substituted or interrupted, R is an organic radical containing at least six carbon atoms, X is a member selected from the group consisting of hydrocarbon and substituted hydrocarbon residues, A is an anion, and the three indicated valence bonds attached to nitrogen are satisfied by radicals of the class consisting of alkyls, cycloalkyls, alkylols, aralkyls, aryls, aralkylols, and the radical of a heterocyclic ring of which the nitrogen is a member, 10 is a small whole number, and R is a member selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkylol, (alkOR) alk, R, x, N-

where and A have the foregoing significance.

l0. Quaternary ammonium-carboxylic esters corraponding to the general formula.

R-COO-Ri in which R denotes an aliphatic radical containing from one to six carbon atoms and at least one quaternary ammonium radical and R1 denotes a radical selected from the group consisting of higher molecular weight carboxylic acid esters andamides of alkylolamines.

11. Quaternary ammonium-carboxylic esters corresponding to the general formula Q-CHa-COO-Rr R-COO-Ri in which R denotes a lower molecular weight radical containing at least one quaternary ammonium radical, and R1 denotes a residue of an alcohol amine containing a lipophile group with at least six carbon atoms.

13. Quaternary ammonium-carboxylic acid esters corresponding to the general formula in which Q is a and R1 denotes a quaternary ammonium radical, residue of an alkylolamine containing a higher molecular weight aliphatic ALBERT K. EPSTE'IN. MORRIS KATZMAN.

radical. 

